JP7097294B2 - Monolith type separation membrane structure - Google Patents

Description

The present invention relates to a monolithic separation membrane structure.

Conventionally, in a monolith type separation film structure including a monolith type base material having a plurality of cells, an intermediate layer formed on the inner surface of each cell, and a separation film formed on the inner surface of the intermediate layer, an intermediate layer is used. A method of suppressing a decrease in the strength of the monolithic separation membrane structure after high-temperature alkali treatment has been proposed by defining the interrelationship between the thickness of the substrate and the thickness of the partition wall of the base material between the two cells (see Patent Document 1). ). In Patent Document 1, the thickness of the intermediate layer is preferably 100 μm or more and 500 μm or less, and the partition wall thickness of the base material is preferably 0.51 mm or more and 1.55 mm or less.

Further, in Patent Document 2, it is said that a partition wall thickness of 0.2 mm or more is preferable in order to prevent the monolith type base material from being significantly deformed and the cell from closing due to firing during manufacturing.

International Publication No. 2012/128218 Japanese Patent No. 5599785

However, depending on the use of the monolith-type separation membrane structure, further compactification and / or weight reduction of the monolith-type separation membrane structure may be desired.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a monolith type separation membrane structure that can be made compact and / or lightweight while maintaining permeation performance.

The monolith-type separation membrane structure according to the present invention includes a monolith-type base material, an intermediate layer, and a separation membrane. The monolith-type substrate has a plurality of filtration cells extending from the first end face to the second end face. The intermediate layer is formed on the inner surface of the filtration cell. The separation membrane is formed on the inner surface of the intermediate layer. The inner diameter of each of the plurality of filtration cells, which does not include the intermediate layer and the separation membrane, is 1.0 mm or more and 2.0 mm or less. The partition wall thickness of the shortest portion of the two adjacent filtration cells among the plurality of filtration cells, excluding the intermediate layer and the separation membrane, is 0.05 mm or more and less than 0.2 mm. The thickness of the intermediate layer is 20 μm or more and less than 100 μm.

According to the present invention, it is possible to provide a monolith type separation membrane structure that can be made compact and / or lightweight while maintaining the permeation performance.

Perspective view of monolith type separation membrane structure Plan view of the first end face AA sectional view of FIG. Schematic diagram showing an example of the state in which the precursor solution of the separation membrane flows in during the manufacturing process.

Next, an embodiment of the present invention will be described with reference to the drawings. In the description of the drawings below, the same or similar parts are designated by the same or similar reference numerals. However, the drawings are schematic, and the ratio of each dimension may differ from the actual one. Therefore, the specific dimensions, etc. should be determined in consideration of the following explanation. In addition, it goes without saying that parts having different dimensional relationships and ratios are included between the drawings.

In the following description, the "monolith" means a shape having a plurality of cells penetrating in the longitudinal direction, and is a concept including a honeycomb.

(Structure of Monolith Type Separation Membrane Structure 100)
FIG. 1 is a perspective view of the monolith type separation membrane structure 100. FIG. 2 is a plan view of the first end surface 11S. FIG. 3 is a sectional view taken along the line AA of FIG.

(Outline of structure)
The monolith-type separation membrane structure 100 shown in FIGS. 1 to 3 comprises a monolith-type base material 10 which is made of a ceramic porous body and has both end faces 11S and 11T and an outer peripheral surface 11U. The outer shape of the monolith type base material 10 is a cylinder. The monolith type base material 10 includes a plurality of filtration cells 24 and a plurality of water collecting cells 25. The plurality of filtration cells 24 are formed in a row (generally laterally in FIG. 1) penetrating from one end face 11S to the other end face 11T. The plurality of water collecting cells 25 are formed in a row (generally laterally in FIG. 1) penetrating from one end face 11S to the other end face 11T.

In the monolith type separation membrane structure 100, the cross-sectional shapes of the filtration cell 24 and the water collecting cell 25 are circular. The filtration cell 24 is open to both end faces 11S and 11T. The water collecting cell 25 is provided with a discharge flow path 26 so that the openings of both end faces 11S and 11T are sealed by the sealing portions 12 and 13 and the water collecting cell 25 communicates with the external space. Further, an intermediate layer 20 and a separation membrane 30 are arranged on the inner wall surface of the filtration cell 24 having a circular cross-sectional shape.

In the monolith type separation membrane structure 100, two discharge flow paths 26 are formed in the vicinity of both end faces 11S and 11T for each row 25L of a plurality of communicating water collecting cells 25. In the monolith-type separation membrane structure 100, the water collecting cells 25 have five rows, and the discharge flow path 26 allows a plurality of water collecting cells 25 to communicate with each other in each row, and the outer peripheral surface of the monolith-type base material 10. It is open to 11U. In FIGS. 1 to 3, since there are five water collecting cell rows 25L in the monolith type separation membrane structure 100, the number of discharge flow paths 26 in the monolith type separation membrane structure 100 is 10 in total at both ends.

With the above configuration, the mixed fluid (liquid mixture or gas mixture) flowing into the filtration cell 24 and the component permeating the filtration cell 24 can be efficiently separated. More specifically, the permeation component that has permeated through the separation membrane 30 on the inner surface of the filtration cell 24 permeates the intermediate layer 20 and sequentially passes through the porous body constituting the inside of the partition wall of the monolith type base material 10. Although it is discharged from the outer wall surface 11U, it is necessary for the inner filtration cell 24 to permeate through the partition wall (porous body) over a long distance. Therefore, by providing the water collecting cell 25 and the discharge flow path 26, the water collecting cell 25 and the discharge flow path 26, which originally have a small pressure loss, are easily passed through the partition wall between the filtration cells 24. It can be discharged to the outside.

In the monolith type separation membrane structure 100, the mixed fluid directly flows in from the porous body portions of both end faces 11S and 11T of the monolith type base material 10, and is separated by the separation membrane 30 formed on the inner wall surface of the predetermined filtration cell 24. In order to prevent the mixed fluid from flowing out without being discharged, the sealing portions 14 and 15 are provided so as to cover the porous bodies of both end faces 11S and 11T of the monolith type base material 10 into which the mixed fluid flows. Both ends of the filtration cell 24 in which the separation membrane 30 is arranged are open so as to be connected to the sealing portions 14 and 15. An intermediate layer 20 and a separation film 30 are sequentially formed on the inner surface of each of the plurality of filtration cells 24.

(Optimal configuration of each structure)
The monolith type base material 10 is formed in a columnar shape. The length of the monolith type base material 10 in the longitudinal direction can be 100 to 2000 mm. The diameter of the monolith type base material 10 can be 30 to 220 mm. The monolith type base material 10 may be an elliptical column or a polygonal column.

The inner diameter C1 excluding the intermediate layer 20 and the separation membrane 30 of the filtration cell 24 is 1.0 mm or more and 2.0 mm or less. By setting the inner diameter C1 to 2.0 mm or less, the filtration cell 24 can be made denser and the total surface area of the separation membrane 30 can be increased to make the monolith type separation membrane structure 100 compact or / or lighter. From the viewpoint of increasing the total surface area, the smaller the inner diameter C1, the higher the density of the filtration cell 24, which is good. Can be. The inner diameter C1 is more preferably 1.10 mm or more and 1.85 mm or less from the viewpoint that it is difficult to cause slurry clogging in production and the total surface area can be increased.

The partition wall thickness D1 of the shortest portion between the two adjacent filtration cells 24, which does not include the intermediate layer 20 and the separation membrane 30, is 0.05 mm or more and less than 0.2 mm. By setting the partition wall thickness D1 of the monolith type base material 10 to less than 0.2 mm, the filtration cells 24 can be made denser and the total surface area of the separation membrane 30 can be increased. From the viewpoint of increasing the total surface area, the smaller the partition wall thickness D1, the higher the density of the filtration cell 24, which is good. Since the inner wall structure may collapse, the thickness can be substantially 0.05 mm or more. The partition wall thickness D1 is more preferably 0.10 mm or more and 0.18 mm or less from the viewpoint that the inner wall structure of the monolith type base material 10 does not easily collapse and the total surface area can be increased.

In the present embodiment, the partition wall thickness D1 is unified at all the locations between the adjacent filtration cells 24, but a plurality of types of partition wall thickness D1 may exist. When a plurality of types of partition wall thicknesses D1 are present, it is preferable that the partition wall thickness D1 is 0.05 mm or more and less than 0.2 mm at 33% or more of all the locations.

The thickness (outer wall thickness D2) of the shortest portion between the outermost filtration cell 24 and the outer peripheral surface 11U, which does not include the intermediate layer 20 and the separation membrane 30, among the plurality of filtration cells 24 is the partition wall thickness between the filtration cells 24. It is preferably 10 times or more and 30 times or less of D1. By setting the outer wall thickness D2 to be 10 times or more the partition wall thickness D1, sufficient strength can be maintained against an external force received by assembly to the device or the like. On the other hand, if the outer wall thickness D2 is unreasonably increased, the effects of compactification and / or weight reduction are offset. Therefore, it is preferable that the outer wall thickness D2 is 30 times or less the partition wall thickness D1. From the viewpoint of withstanding an external force due to assembly or the like, the compressive strength of the monolith type separation membrane structure 100 in the longitudinal direction is preferably 5 MPa or more.

As shown in FIG. 2, when the first end surface 11S is viewed in a plan view, the plurality of filtration cells 24 form a plurality of filtration cell rows 24L. Each of the plurality of filtration cell rows 24L includes two or more filtration cells 24 arranged along the lateral direction (an example of a predetermined direction) orthogonal to the longitudinal direction. In the present embodiment, 28 rows of filtration cell rows 24L are formed, and 7 to 29 filtration cells 24 are lined up in each row. However, the number of rows of the filtration cell rows 24L and the filtration included in each row The number of cells 24 can be changed as appropriate.

As shown in FIG. 3, the water collecting cell 25 is formed along the longitudinal direction of the monolith type base material 10. Both ends of the water collecting cell 25 are sealed by the first sealing portion 12 and the second sealing portion 13, and do not open to the first sealing portion 14 and the second sealing portion 15. The intermediate layer 20 and the separation membrane 30 are not formed on the inner surface of the water collecting cell 25.

The inner diameter C2 of the water collecting cell 25 can be 0.5 mm or more and 3.0 mm or less. From the viewpoint of increasing the total surface area, the smaller the inner diameter C2 is, the higher the density of the filtration cell 24 is, but from the viewpoint of reducing the permeation resistance of the permeation separation component, the larger the inner diameter C2 is, the better. It is appropriately selected depending on the usage conditions of the type separation membrane structure 100. From the viewpoint of ease of manufacture, the inner diameter C2 is preferably 1.0 mm or more and 2.0 mm or less. The inner diameter C2 may be the same as or different from the inner diameter C1 that does not include the intermediate layer 20 and the separation membrane 30 of the filtration cell 24.

The partition wall thickness D3 of the shortest portion of the adjacent filtration cell 24 and the catchment cell 25, which does not include the intermediate layer 20 and the separation membrane 30, can be 0.05 mm or more and less than 0.2 mm. By setting the partition wall thickness D3 to less than 0.2 mm, the total surface area can be increased. From the viewpoint of increasing the total surface area, the smaller the partition wall thickness D3, the higher the density of the filtration cell 24, which is good. Since the inner wall structure may collapse, the thickness can be substantially 0.05 mm or more. The partition wall thickness D3 is more preferably 0.1 mm or more and 0.18 mm or less from the viewpoint that the inner wall structure of the monolith type base material 10 does not easily collapse and the total surface area can be increased. Further, although not shown, the distance between adjacent water collecting cells 25 can also be 0.05 mm or more and less than 0.2 mm, and more preferably 0.1 mm or more and 0.18 mm or less.

In the present embodiment, the partition wall thickness D3 is unified at all points between the adjacent filtration cell 24 and the water collecting cell 25, but a plurality of types of partition wall thickness D3 may exist. When a plurality of types of partition wall thicknesses D3 are present, it is preferable that the partition wall thickness D3 is 0.05 mm or more and less than 0.2 mm at 33% or more of all the locations.

As shown in FIG. 2, when the first end surface 11S is viewed in a plan view, the plurality of water collecting cells 25 form a plurality of water collecting cell rows 25L. Each of the plurality of water collecting cell rows 25L includes two or more water collecting cells 25 arranged along the lateral direction (an example of a predetermined direction). In the present embodiment, five rows of water collecting cell rows 25L are arranged at positions separated from each other, and 22 to 29 water collecting cells 25 are lined up in each row, but the position of the water collecting cell row 25L. The number of rows and the number of catchment cells 25 included in each row can be changed as appropriate.

Between the two rows of water collecting cell rows 25L, four rows or five rows of filtration cell rows 24L are arranged. That is, four rows or five rows of filtration cell rows 24L are arranged on both sides of one row of water collecting cell rows 25L. The number of rows of the filtration cell rows 24L arranged between the two rows of water collecting cell rows 25L (the number of filtration cell rows between the collecting cell rows) is preferably 2 rows or more and 9 rows or less. By setting the number of filtration cell rows between the collection cell rows to 9 or less, from the filtration cell 24 located on the innermost side to the water collection cell 25 among the filtration cells 24 located between the water collection cell rows 25L. It is possible to shorten the flow distance of the permeation component of.

Here, from the viewpoint that the rate-determining flow of the permeated component can be suppressed, the smaller the number of filtration cell rows between the collecting cell rows is, the better, but by reducing the number, the number of collecting cells 25 is relatively increased. The number of filtration cells 24 is reduced, which reduces the total surface area of the separation membrane 30. From the viewpoint that the total surface area of the separation membrane 30 is not excessively reduced from the predetermined amount, it is preferable that the number of filtration cell rows between the collection cell rows is two or more. From the viewpoint of reducing the pressure loss of the permeated component from the filtration cell 24 to the water collection cell 25 and maintaining a high total surface area of the separation film 30, the number of filtration cell rows between the water collection cells is 4. It is particularly preferable that the number of rows is 6 or more.

As shown in FIG. 1, the discharge flow path 26 has an opening 26a that opens to the outer peripheral surface 11U. The width W1 of the opening 26a in the circumferential direction about the axis AX of the monolith type base material 10 can be 10% or more and 80% or less of the inner diameter C2 of the water collecting cell 25, and the area of the opening 26a can be increased. It is preferably 16% or more of the inner diameter C2 from the viewpoint of increasing the pressure loss of the permeation component and 50% or less from the viewpoint of easy cutting in manufacturing.

The total length L1 of the two openings 26a in the longitudinal direction of the monolith type substrate 10 (that is, L1 + L1) shall be 3.3% or more and 40% or less of the total length L2 of the monolith type substrate 10 in the longitudinal direction. It is preferable that the total length is 9% or more from the viewpoint of increasing the area of the opening 26a and reducing the pressure loss of the permeation component, and 17% or less from the viewpoint of the mechanical strength of the monolith type separation film structure 100. Is preferable. As a result, the pressure loss of the permeation component (fluid) collected in the water collecting cell 25 can be reduced, so that the permeation rate of the permeation component can be improved.

Here, the opening 26a may be arranged at only one of both ends, or may be bored in the middle of the longitudinal direction in addition to both ends. From the viewpoint of evenly discharging the permeated components, it is preferable that they are arranged at least at both ends. Further, when a plurality of openings are installed, the lengths of the openings may be the same or different. The number, shape, and position of the discharge flow paths 26 may be the same or different in the total collection cell row 25L.

The first sealing 12 and the second sealing 13 are arranged in all the collecting cells 25. The first sealing 12 and the second sealing 13 are arranged to face each other at both ends of each water collecting cell 25. The first sealing 12 and the second sealing 13 can be made of a porous material. The filling depth of the first sealing 12 and the second sealing 13 can be about 5 to 20 mm.

The first seal portion 14 covers the entire surface of the first end surface 11S and a part of the outer peripheral surface 11U. The first sealing portion 14 suppresses the infiltration of the mixed fluid into the first end surface 11S. The first seal portion 14 is formed so as not to block the inflow port of the filtration cell 24. The first sealing portion 14 covers the first sealing portion 12. As the material constituting the first sealing portion 14, glass, metal, rubber, resin or the like can be used, and glass is suitable in consideration of the consistency with the coefficient of thermal expansion of the monolith type base material 10.

The second seal portion 15 covers the entire surface of the second end surface 11T and a part of the outer peripheral surface 11U. The second sealing portion 15 suppresses the infiltration of the mixed fluid into the second end surface 11T. The second seal portion 15 is formed so as not to block the outlet of the filtration cell 24. The second sealing portion 15 covers the second sealing portion 13. The second seal portion 15 can be made of the same material as the first seal portion 14.

(Monolith type base material 10)
Next, the monolith type base material 10 will be described.

The monolith type base material 10 contains an aggregate and a binder. As the aggregate, alumina, silicon carbide, titania, mullite, cerben, cordierite and the like can be used. The binder is an inorganic oxide material that melts at a temperature lower than that of the aggregate component and connects the aggregates to each other. As the binder, an alumina-based inorganic oxide material containing an alkali metal, an alkaline earth metal, or the like can be used.

The content of the aggregate in the monolith type base material 10 can be 60% by volume or more and 80% by volume or less, preferably 65% by volume or more and 75% by volume or less. The content of aggregate can be measured by the Archimedes method.

The oxide material as a binder is a glass material containing at least one of an alkali metal and an alkaline earth metal, silicon (Si), and aluminum (Al). As the alkali metal, at least one of sodium (Na), potassium (K) and lithium (Li) can be used. The oxide material may contain an alkali metal as an alkali metal oxide. As the alkaline earth metal, at least one of magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba) can be used. The oxide material may contain an alkaline earth metal as an alkaline earth metal oxide. The oxide material preferably contains both alkali metals and alkaline earth metals. The oxide material may contain Si as SiO ₂ . The oxide material may contain Al as Al ₂ O ₃ .

The content of the oxide material in the monolith type base material 10 can be 20% by volume or more and 40% by volume or less, preferably 25% by volume or more and 35% by volume or less. Oxide Material Content The oxide material content can also be measured by the Archimedes method.

The porosity of the monolith type base material 10 is not particularly limited, but can be 25% to 50%, preferably 30% to 45%. The porosity of the monolith type base material 10 can be measured by a mercury intrusion method.

The average pore diameter of the monolith type base material 10 is not particularly limited, but can be 0.1 μm to 50 μm, and is more preferably 1 μm to 10 μm from the viewpoint that the intermediate layer 20 can be easily formed. ..

(Middle layer 20)
The intermediate layer 20 is formed on the inner surface of the filtration cell 24. The intermediate layer 20 is formed in a tubular shape.

The intermediate layer 20 contains an aggregate and a binder. As the aggregate, alumina, titania, mullite, cerben, cordierite and the like can be used. The binder is an inorganic component that is sintered and solidified at a temperature at which the aggregate component does not sinter. As the binder, easily sinterable alumina, silica, glass frit, clay mineral, easily sinterable cordierite and the like can be used.

The ratio of the binder in the inorganic solid content (aggregate + binder) in the intermediate layer 20 can be 5% by mass or more and 42% by mass or less, and 28% by mass from the viewpoint that the intermediate layer 20 has high strength. 42% by mass or more is preferable, and 30% by mass or more and 42% by mass or less is more preferable.

As shown in FIG. 3, the intermediate layer 20 according to the present embodiment has a first intermediate layer 21 and a second intermediate layer 22. The first intermediate layer 21 is formed on the inner surface of the filtration cell 24 of the monolith type base material 10. The second intermediate layer 22 is formed on the inner surface of the first intermediate layer 21. The average pore diameter of the second intermediate layer 22 is preferably smaller than the average pore diameter of the first intermediate layer 21. For example, when the average pore diameter of the first intermediate layer 21 is about 1 μm, the average pore diameter of the second intermediate layer 22 can be about 0.1 μm.

The intermediate layer 20 is not limited to the two-layer structure of the first intermediate layer 21 and the second intermediate layer 22, but may be a single-layer structure composed of one intermediate layer having a uniform average pore diameter. However, it may have a multilayer structure composed of three or more intermediate layers having a smaller average pore diameter as it is closer to the separation film 30.

The thickness E1 of the intermediate layer 20 is 20 μm or more and less than 100 μm. By setting the thickness E1 of the intermediate layer 20 to less than 100 μm, the surface area of the separation membrane 30 can be increased. From the viewpoint of increasing the surface area, the smaller the thickness E1 of the intermediate layer 20, the better, and it is desirable that it is less than 100 μm. However, if it is too small, the surface of the intermediate layer 20 is not sufficiently smoothed and defects are likely to occur. Therefore, it can be substantially 20 μm or more. From the viewpoint of increasing the surface area of the separation membrane 30 as much as possible while suppressing the frequency of defects due to defects, the thickness E1 of the intermediate layer 20 is more preferably 40 μm or more and less than 80 μm.

(Separation membrane 30)
The separation membrane 30 is formed on the inner surface of the intermediate layer 20. The separation membrane 30 is formed in a tubular shape. The separation membrane 30 allows the permeation separation component contained in the mixed fluid to permeate. The separation function of the monolith type separation membrane structure 100 is exhibited by the separation membrane 30. The average pore diameter of the separation membrane 30 can be appropriately determined based on the required filtration performance and separation performance. For example, the average pore diameter of the separation membrane 30 can be, for example, 0.0003 μm (0.3 nm) to 1.0 μm, but is not particularly limited. The average pore diameter of the separation membrane 30 can be measured by the airflow method described in ASTM F316.

As the separation membrane 30, a known MF (microfiltration) membrane, UF (ultrafiltration) membrane, gas separation membrane, osmotic vaporization membrane, steam permeable membrane, or the like can be used. Specifically, the separation membrane 30 includes a ceramic membrane (see, for example, JP-A-3-267129 and JP-A-2008-246304), a carbon monoxide separation membrane (see, for example, Patent No. 4006107), and helium. Separation membrane (see, for example, Patent No. 3953833), hydrogen separation membrane (see, for example, Patent No. 3933907), carbon membrane (see, for example, JP-A-2003-286018), zeolite membrane (see, for example, JP-A-2004). -66188 (see, for example, International Publication No. 2008/050812), organic-inorganic hybrid silica film (Japanese Patent Laid-Open No. 2013-203618), p-tolyl group-containing silica film (Japanese Patent Laid-Open No. 2013-2013). No. 226541) and the like.

The inner diameter E2 of the separation membrane 30 can be 0.8 mm or more and 1.96 mm or less. The inner diameter E2 is preferably 1.2 mm or more and 1.8 mm or less from the viewpoint that the mixed fluid to be separated can be easily circulated and the total evaluation area of the separation membrane 30 can be increased. The inner diameter E2 is the maximum inner diameter of the separation membrane 30. The sum of the total surface areas of the separation membranes 30 in each filtration cell 24 is the "membrane area" of the monolith type separation membrane structure 100.

As described above, in the monolith type separation membrane structure 100 according to the present embodiment, the inner diameter C1 of the filtration cell 24 is 1.0 mm or more and 2.0 mm or less, and the partition wall thickness D1 between the adjacent filtration cells 24 is 0. It is 05 mm or more and less than 0.2 mm, and the thickness E1 of the intermediate layer 20 is 20 μm or more and less than 100 μm. Therefore, since the total area of the separation membrane 30 can be increased, the area of the separation membrane 30 per unit volume of the monolith type separation membrane structure 100 is set to 1 m ² / L or more, and the unit of the monolith type separation membrane structure 100 is set to 1 m 2 / L or more. The area of the separation membrane 30 per weight can be 0.5 m ² / kg or more. As a result, the monolith-type separation membrane structure 100 can be made compact or / or lightweight while maintaining the permeation performance of the monolith-type separation membrane structure 100.

(Manufacturing method of monolith type separation membrane structure 100)
First, the raw material of the monolith type base material 10 is extruded using, for example, a vacuum extrusion molding machine to obtain a monolith type molded body having a filtration cell 24 and a water collecting cell 25. Examples of the raw material of the monolith type base material 10 include clay prepared by adding an organic binder such as methyl cellulose, a dispersant and water to aggregate particles and an inorganic binder and kneading them. As the aggregate particles, specifically, at least one ceramic material selected from the group consisting of alumina, silicon carbide, mullite, cerben, and cordierite can be preferably used.

At this time, the average particle size of the aggregate particles used can be 5 μm or more and less than 40 μm. This is because if it is larger than 40 μm, when the monolith type base material 10 having a thin partition wall thickness is extruded as in the present invention, the base may be clogged with clay and molded. On the other hand, if it is 5 μm or less, the material strength may be insufficient and the structure of the monolith type base material 10 may not be maintained. From the viewpoint that the monolith type base material 10 having a thin partition wall thickness of the present invention can be more preferably extruded, the average particle size of the aggregate particles is more preferably 10 μm or more and 25 μm or less.

The oxide material as an inorganic binder is a glass material containing at least one of an alkali metal and an alkaline earth metal, silicon (Si), and aluminum (Al). As the alkali metal, at least one of sodium (Na), potassium (K) and lithium (Li) can be used. As the alkaline earth metal, at least one of magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba) can be used. The oxide material preferably contains both alkali metals and alkaline earth metals. The oxide material may contain Si as SiO ₂ . The oxide material may contain Al as Al ₂ O ₃ . Specifically, natural raw materials such as kaolin, talc, feldspar, dolomite, clay, and silica sand may be used, or industrial raw materials such as fused alumina, silica, and calcium carbonate may be used, and these may be mixed. You may use it.

The average particle size of the inorganic binder used can be 0.1 μm or more and 10 μm or less. When it is 10 μm or less, it is possible to provide a monolith type base material 10 which is easily melted by firing and / or is highly dispersed among aggregate particles and has high strength. From the viewpoint of being able to disperse more among the aggregate particles, it is better that the average particle size of the inorganic binder is small, but the finer the raw material, the higher the cost tends to be, so the average particle size should be substantially 0.1 μm or more. be able to. From the viewpoint of being used together with the above-mentioned aggregate particles having an average particle size of 10 μm or more and 25 μm or less, the average particle size of the inorganic binder is more preferably 0.5 μm or more and 5 μm or less.

Then, the obtained monolith-shaped molded body is fired at, for example, 900 to 1600 ° C. to obtain a monolith-type base material, and the monolith-shaped molded body is communicated from one part of the outer peripheral surface thereof through the water collecting cell 25 to another part. The discharge flow path 26 is formed to obtain a monolith type base material on which the discharge flow path 26 is formed. The notch for the discharge flow path is formed, for example, by cutting with a band saw, a disc cutter, a wire saw or the like provided with diamond abrasive grains while aiming the laser aiming at both end surfaces on which the discharge flow path 26 should be formed. Can be done. During the cutting, the friction between the monolith type base material and the cutting tool causes the diamond abrasive grains to degrain and / or generate heat, which shortens the life of the cutting tool. Or / and the heat can be reduced.

In order to make the width W1 of the discharge flow path 26 suitable, the thickness of a cutting tool such as a band saw, a disc cutter, or a wire saw can be selected, and at that time, the cutting allowance is divided with respect to the target width W1. Can be reduced to a thickness. For example, when the width W1 of the discharge flow path 26 is aimed at 0.8 mm, a diamond disc having a thickness of 0.6 mm obtained by subtracting the cutting allowance can be selected. The width W1 is more preferably 50% or less of the inner diameter C2 of the water collecting cell 25 forming the discharge flow path 26 from the viewpoint of easy cutting. This is because if the ratio of the width W1 to the inner diameter C2 is large, the partition wall between the filtration cell 24 and the water collecting cell 25 may be pierced depending on the accuracy of laser aiming and the processing accuracy at the time of cutting.

In cutting the discharge flow path 26, a suitable length L1 of the discharge flow path 26 can be selected by adjusting the cutting distance in the longitudinal direction. The cutting speed to be cut is appropriately selected in consideration of the strength of the monolith type base material, the generated frictional heat, and the like, but can be 0.1 to 50 mm / sec. If it is 0.1 mm / sec or less, it is not preferable because it takes too much cutting time, and if it is 50 mm / sec or more, it is not preferable because excessive stress may be applied to the monolith type base material to damage it. The cutting speed is more preferably 0.5 to 10 mm / sec from the viewpoint that the life of the processing tool is not shortened and the processing can be easily performed.

Depending on the cutting tool used, the cutting surface of the drainage flow path 26 is not straight, and may be fan-shaped inside, especially when a disc cutter is used. In this case, it is formed on the outer peripheral surface 11U. The opening length is defined as the length L1 of the opening 26a. Further, in order to make the discharge of the permeated component suitable, it is also possible to provide a discharge flow path in the body portion other than both ends by using a drill, a lutor, a water cutter or the like.

Next, in the obtained monolith-type base material, a sealing member is filled in the space from both end faces of the water collecting cell in which the notch for the discharge flow path is formed to reach the discharge flow path 26.

Specifically, a film (masking) such as polyester is attached to both end faces of the monolith type base material, and holes are formed in the film by laser irradiation or the like in the portion corresponding to the discharge flow path 26. After that, the end face to which the film of the monolith type base material is attached is pressed into the container filled with the sealing member (slurry), and further pressed by an air cylinder or the like with, for example, 200 kg, and filled. Then, the obtained unfired monolith type base material filled with a sealing member is fired at, for example, 900 to 1400 ° C. to obtain a monolith type base material filled with a sealing member.

Then, an intermediate layer 20 serving as a base for the separation film 30 is formed on the inner wall surface of the filtration cell 24 of the monolith type base material filled with the sealing member. In order to form (deposit) the intermediate layer 20, first, a slurry for the intermediate layer is prepared. The slurry for the intermediate layer is prepared by adding 400 parts by mass of water to 100 parts by mass of a ceramic raw material having a desired particle size (for example, an average particle size of 1 to 5 μm) such as alumina, mullite, titania, and cordierite. Can be done.

Further, an inorganic binder for a membrane may be added to the intermediate layer slurry in order to increase the membrane strength after sintering. As the inorganic binder for the membrane, clay, kaolin, titania sol, silica sol, glass frit and the like can be used. The amount of the inorganic binder for a membrane added is preferably 5 to 42 parts by mass from the viewpoint of membrane strength. This slurry for an intermediate layer (for example, using the apparatus disclosed in Japanese Patent Application Laid-Open No. 61-238315) is attached to the inner wall surface of the filtration cell 24, dried, and then sintered at, for example, 900 to 1050 ° C. The intermediate layer 20 can be formed by forming the intermediate layer 20.

The intermediate layer 20 can be divided into a plurality of layers such as the intermediate layer 21 and the intermediate layer 22 by using a plurality of types of slurry having different average particle sizes, and the monolith type of the present invention can be formed. Like the separation membrane structure 100, it may have, for example, a plurality of intermediate layers 20. When forming a film of the intermediate layer 20 having a plurality of layers, the film forming step and the firing step may be performed for each intermediate layer, or the film forming step may be repeated and then fired as a unit. By disposing the separation film 30 on the intermediate layer 20, the influence of the unevenness on the surface of the monolith type base material can be reduced by the intermediate film 20. As a result, even if the separation membrane 30 is made into a thin film, defects can be reduced. That is, it is possible to obtain a monolith type separation membrane structure 100 having high flux, low cost, and high separation ability.

Next, the glass raw material slurry was applied to the end face of the obtained monolith type substrate with an intermediate layer by spray spraying or brushing, and then fired at, for example, 800 to 1000 ° C. to obtain the first and second sealing portions 14. , 15 to form a molded body. The glass raw material slurry is prepared, for example, by mixing water and an organic binder in a glass frit. The case where the material of the first and second sealing portions 14 and 15 is glass has been described above, but the first and second sealing portions 14 and 15 are separated from the mixed fluid to be separated from the discharge flow path 26. Any material may be used as long as it does not allow the discharged separation fluid to pass through, and for example, a silicon resin, a Teflon (registered trademark) resin, or the like may be used. When the intermediate layer 20 has a multi-layer structure, the molded bodies of the first and second sealing portions 14 and 15 may be formed during the formation of the intermediate layer 20.

Next, the separation film 30 is formed on the inner surface of the intermediate layer 20. Here, when the average pore diameter of the separation membrane 30 is smaller than 1 nm and further thinning is required to reduce the pressure loss, it is preferable to further dispose an underlayer between the intermediate layer 20 and the separation membrane 30. .. For example, on the intermediate layer 20, titanium isopropoxide is hydrolyzed in the presence of nitric acid to obtain a titania sol solution, diluted with water to prepare a sol for an underlayer, and the prepared sol for an underlayer is used as an intermediate. It is desirable to form a base layer by, for example, heat-treating at 400 to 500 ° C. after circulating on the inner wall surface of a predetermined cell of the monolith type base material with a layer.

When the separation film 30 is a silica film, the precursor solution (silica sol solution) is prepared by hydrolyzing an organic silane compound in the presence of nitric acid to obtain a sol solution, and diluting it with an organic solvent such as ethanol. Can be done. It is also possible to dilute with water instead of diluting with an organic solvent. Then, for example, as shown in FIG. 4, the outer peripheral surface 11U of the monolith type base material 10 on which the base layer is formed is sealed with a masking tape 71, and the first end surface 11S is fixed to the lower end of a wide-mouthed funnel (not shown). A precursor solution 70 (silica sol solution) to be a silica film is poured from above the monolith type substrate 10 and passed through the surface (underlayer) of the filtration cell 24, or the precursor solution 70 is subjected to general dipping. , Adhere to the surface (base layer) of the filtration cell 24. Then, the temperature is raised at 100 ° C./hour, held at 350 to 500 ° C. for 1 hour, and then lowered at 100 ° C./hour. The silica film can be arranged by repeating such operations of pouring, drying, raising the temperature, and lowering the temperature 1 to 5 times. As described above, a monolith type separation membrane structure in which the separation membrane 30 is a silica membrane can be obtained.

As a method for forming the separation membrane 30, an appropriate method according to the type of the separation membrane 30 may be used as described above. In the present specification, the method for producing the separation membrane 30 described in each of the above-mentioned publications is referred to.

(Other embodiments)
Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment, and various modifications can be made without departing from the gist of the invention.

The monolith type separation membrane structure 100 is provided with the filtration cell 24 and the water collecting cell 25, but the water collecting cell 25 may not be provided. In this case, the monolith type separation membrane structure 100 does not have to include the discharge flow path 26.

It is assumed that the inner diameters C1 of the filtration cells 24 are all equal, but the inner diameter C1 is not limited to this. It is assumed that the inner diameters C2 of the water collecting cells 25 are all equal, but the inner diameter C2 is not limited to this.

Although it was decided that each of the first and second seal portions 14 and 15 covers a part of the outer peripheral surface 11U, it does not have to cover the outer peripheral surface 11U.

Hereinafter, examples of the monolith type separation membrane structure according to the present invention will be described. However, the present invention is not limited to the examples described below.

(Preparation of Examples 1 to 3, 5 to 11)
The monolith type separation membrane structure according to Examples 1 to 3, 5 to 11 was prepared as follows.

First, 30% by volume of an inorganic binder is added to 70% by volume of alumina particles (aggregate) having an average particle size of 12 μm, and if necessary, a molding aid such as an organic binder or a pore-forming agent is added to dry type. After mixing, water and a surfactant were added, and the mixture was mixed and kneaded to prepare a clay. As the inorganic binder, talc, kaolin, feldspar, clay and the like having an average particle size of 1 to 5 μm are used as SiO ₂ (70% by mass), Al ₂ O ₃ (16% by mass), alkaline earth metal and alkali metal (alkaline metal). 11% by mass) was appropriately mixed so as to have the target content.

Next, the clay was extruded to create a monolithic molded body having a large number of cells. The obtained molded product was calcined (1250 ° C., 1 hour) to obtain a monolith type substrate. The size of the monolith type base material after firing was 63 mm in diameter × 300 mm in length.

Next, cuts were made with a diamond disc cutter along the water collecting cell rows on both end faces of the monolith type base material. At this time, by adjusting the thickness of the diamond disc and the cutting distance in the longitudinal direction, the total width and length of the opening of the discharge flow path was changed as shown in Table 1. In addition, the position where the cut is made is an embodiment so that the number of columns of the filtration cell rows (the number of filtration cell rows between the water collection cell rows) arranged between the two collection cell rows is as shown in Table 1. I changed it every time.

Next, polyester films were attached to both end faces of the monolith type base material, and holes were formed in the portions corresponding to the water collecting cell rows by laser irradiation.

Next, both ends of the monolith type base material were pressed against the slurry-state sealing member. As the sealing member, a glass binder was added to the main component alumina aggregate, and water and a binder were further added and mixed.

Next, the monolith-type base material filled with the sealing member was fired (950 ° C. for 1 hour) to obtain a monolith-type base material filled with the sealing member.

The total of the inner diameter of the filtration cell, the thickness of the partition wall, the thickness of the outer wall, the opening width and the opening length of the discharge flow path opened on the outer peripheral surface of the main body is as shown in Table 1. The inner diameter of the water collecting cell, the partition wall thickness between the water collecting cells, and the partition wall thickness between the filtration cell and the water collecting cell were the same as those of the filtration cell.

Next, 14 parts by mass of an inorganic binder is added to 100 parts by mass of alumina particles (aggregate) having an average particle size of 2.3 μm, and water, a dispersant, and a thickener are further added and mixed. 1 A slurry for an intermediate layer was prepared. Using the slurry, the slurry was adhered to the inner peripheral surface of the through hole for the filtration cell by the filtration film forming method described in Japanese Patent Publication No. 63-66566. Then, the first intermediate layer was formed by firing in an electric furnace (950 ° C., 1 hour) in an atmospheric atmosphere. The inorganic binders include SiO ₂ (77 mol%), ZrO ₂ (10 mol%), LiO ₂ (3.5 mol%), Na ₂ O (4 mol%), and K ₂ O (4 mol%). ), CaO (0.7 mol%) and MgO (0.8 mol%) were melted and homogenized at 1600 ° C., cooled and then pulverized to an average particle size of 1 μm. I used the one.

Next, 20 parts by mass of an inorganic binder is added to 100 parts by mass of titania particles (aggregate) having an average particle size of 0.3 μm, and an organic binder, a pH adjuster, a surfactant and the like are mixed to form a second intermediate. A layer slurry was prepared.

Next, the slurry for the second intermediate layer was deposited on the inner surface of the first intermediate layer by a filtration method to form a molded product of the second intermediate layer.

Next, the second intermediate layer was formed by firing the molded product of the second intermediate layer (950 ° C., 1 hour).

Next, a glass raw material slurry was applied to the end face of the monolith type base material with an intermediate layer by spray spraying, and then fired (950 ° C., 1 hour) to form a sealed portion on the end face.

Next, titanium isopropoxide was hydrolyzed in the presence of nitric acid to obtain a titania sol solution, which was diluted with water to prepare a slurry for the third intermediate layer (underlayer).

Next, the slurry for the third intermediate layer was circulated on the inner surface of the second intermediate layer, and then heat-treated (425 ° C., 1 hour) to form the third intermediate layer.

The total thickness of the first intermediate layer, the second intermediate layer and the third intermediate layer (hereinafter collectively referred to as "intermediate layer") was as shown in Table 1.

Next, p-tolyltrimethoxysilane was hydrolyzed in the presence of nitric acid to obtain a silica sol solution, which was diluted with ethanol to prepare a precursor solution for a separation membrane.

Next, a separation membrane was formed by circulating a precursor solution for a separation membrane on the inner surface of the third intermediate layer and then heat-treating (400 ° C., 1 hour).

(Preparation of Examples 4 and 12)
In Examples 4 and 12, in the process of producing the monolith base material, (1) 60% by volume of alumina particles (aggregate) having an average particle size of 12 μm was added with 40% by volume of an inorganic binder, and (2) inorganic. As the binder, talc, kaolin, slag stone, clay, etc. having an average particle size of 1 to 5 μm are used as SiO ₂ (14% by mass), Al ₂ O ₃ (80% by mass), alkaline earth metal and alkali metal (3% by mass). %) The same steps as in Examples 1 to 3, 5 to 11 except that an appropriate mixture was used so that the desired content was obtained, and (3) the firing conditions were set to 1525 ° C. for 1 hour. A monolithic separation membrane structure was prepared in the above.

As described above, the monolith type separation membrane structure according to Examples 1 to 12 was completed. The area of the separation membrane per unit volume of the monolith type separation membrane structure and the area of the separation membrane per unit weight of the monolith type separation membrane structure are as shown in Table 1.

(Preparation of Comparative Example 1)
In Comparative Example 1, in the preparation of clay, 20% by volume of an inorganic binder was added to 80% by volume of alumina particles (aggregate) having an average particle size of 80 μm, and in extrusion molding, the inner diameter of the filtration cell and the partition wall were added. A monolith type separation film structure was produced in the same steps as in Examples 1 to 12 except that the thickness and the thickness of the intermediate layer were increased as shown in Table 1.

(Preparation of Comparative Example 2)
In Comparative Example 2, when the inner diameter was set to 0.9 mm in extrusion molding in order to increase the number of filtration cells as shown in Table 1, the slurry for the intermediate layer was clogged inside the filtration cells in the film formation of the intermediate layer. The intermediate layer could not be formed because it had been extruded.

(Preparation of Comparative Example 3)
In Comparative Example 3, when the partition wall thickness was set to 0.04 mm, the monolith structure could not be maintained and the monolith type base material could not be formed due to insufficient strength due to the partition wall thickness being too thin in extrusion molding.

(Preparation of Comparative Example 4)
In Comparative Example 4, a monolith type separation membrane structure was produced in the same steps as in Examples 1 to 12 except that the thickness of the intermediate layer was reduced as shown in Table 1.

(Ethanol permeability test)
The monolithic separation membrane structures of Examples 1 to 12 and Comparative Examples 1 and 4 were incorporated into a separation device, and an organic solvent (n-octane: 33% by volume, p-xylene: 33% by volume) and ethanol (33% by volume) were incorporated. The outer circumference of the monolithic separation membrane structure was depressurized to 45 Torr while flowing the mixed fluid of the above into the filtration cell inside the separation membrane.

Then, the ethanol that permeates the separation membrane and flows out from the opening of the discharge channel is recovered, the permeation rate of ethanol is calculated based on the mass of the recovered ethanol and the separation treatment time, and the permeation concentration of the recovered ethanol is calculated. Was measured.

(Isostatic strength test)
Isostatic of monolithic separation membrane structures of Examples 1 to 12 and Comparative Examples 1 and 4 according to the method for measuring isostatic fracture strength specified in JASO standard M505-87, which is an automobile standard issued by the Society of Automotive Engineers of Japan. The static intensity was measured. Isostatic strength is the fracture strength measured by applying hydrostatic pressure in water.

In Table 1, those that were not destroyed even when 20 MPa was applied were evaluated as “◯ (good)”, and those that were destroyed at 5 MPa or more and less than 20 MPa were evaluated as “Δ (possible)”.

As shown in Table 1, in Examples 1 to 12, the separation membrane area per unit volume and the separation membrane area per unit weight could be improved as compared with Comparative Example 1 (conventional example). This is because the inner diameter of the filtration cell is reduced from the conventional 2.2 mm to 2.0 mm or less, the partition wall thickness is reduced from the conventional 0.8 mm to less than 0.2 mm, and the thickness of the intermediate layer is reduced from the conventional 170 μm. This is because the total area of the separation membrane could be increased by making it less than 100 μm.

From the viewpoint of increasing the separation membrane area, it is preferable that the inner diameter of the filtration cell, the thickness of the partition wall, and the thickness of the intermediate layer are small. Therefore, in Example 3, the inner diameter was reduced from 1.85 mm to 1.10 mm, the partition wall thickness was reduced from 0.15 mm to 0.05 mm, and the thickness of the intermediate layer was reduced from 70 μm to 20 μm as compared with Example 1. The area could be significantly improved and the permeation speed could be improved. In Example 3, since the inner diameter of the water collecting cell was also reduced to 1.10 mm at the same time, the opening width was reduced from 0.8 mm to 0.3 mm in order to facilitate the processing of the discharge flow path.

On the other hand, if the inner diameter of the filtration cell, the thickness of the partition wall, and the intermediate layer are made too small, problems will occur. When the inner diameter of the filter cell was reduced to 0.9 mm as in Comparative Example 2, the intermediate layer could not be formed because the slurry for the intermediate layer was clogged inside the filter cell in the film formation of the intermediate layer. When the partition wall thickness was 0.04 mm as in Comparative Example 3, the monolith structure could not be maintained and the monolith type base material could not be formed due to insufficient strength due to the inner wall being too thin in extrusion molding. When the thickness of the intermediate layer is 15 μm as in Comparative Example 4, the surface of the filtration cell cannot be sufficiently smoothed and / or the surface cannot be covered, so that a defect occurs in the separation film formed on the intermediate layer. It could hardly be concentrated (it had the same concentration as the original mixed fluid).

Further, in Examples 1 to 12, the permeation concentration of ethanol could be increased as compared with Comparative Example 4. This is because the defect of the separation membrane could be suppressed by ensuring the thickness of the intermediate layer and smoothing the surface.

It should be noted that Example 4 is necessary even if the inner diameter of the filtration cell, the thickness of the partition wall, the thickness of the intermediate layer, and the material density are each the most disadvantageous to the membrane area, as long as they are within the design range of the present application. It shows that the transmission performance can be maintained.

Based on the above, the partition thickness is 0.05 mm or more and less than 0.2 mm, the thickness of the intermediate layer is 20 μm or more and less than 100 μm, and the inner diameter of the through hole for the filtration cell is 1.0 mm or more and 2.0 mm or less. It was confirmed that the monolith type separation membrane structure can be made compact and / or lightweight while maintaining the permeation performance.

Next, the number of filtration cell rows between the collection cell rows will be described.

In Example 6, the permeation rate of ethanol could be further improved as compared with Example 8. This is because the pressure loss can be reduced by shortening the distance through which the ethanol separated on the surface of the separation membrane permeates through the partition wall by reducing the number of filtration cell rows between the collection cell rows to 9 rows or less. .. From the viewpoint of reducing the pressure loss, the smaller the number of filtration cell rows between the collecting cell rows is, the better, so that the permeation rate is further improved in Example 1.

On the other hand, reducing the number of filtration cell rows between the collection cell rows increases the number of water collection cell rows, so that the number of water collection cells relatively increases and the number of filtration cells decreases, resulting in a separation membrane. Will reduce the surface area of. Therefore, in Example 5, although the number of filtration cell rows between the collection cell rows was smaller than that in Example 1, the permeation rate decreased. This is because the effect of reducing the film area is greater than the effect of reducing the pressure loss.

Further, in Example 7, since the number of filtration cell rows between the collection cell rows was set to 1, the number of filtration cells was significantly reduced and the membrane area was reduced, so that the permeation rate was lowered. From the above results, from the viewpoint of reducing the pressure loss when ethanol permeates and maintaining a high surface area of the separation membrane, the number of filtration cell rows between the collecting cell rows should be 4 or more and 6 or less. Was found to be particularly preferable.

Next, the sum of the slit opening width and the opening length will be described. In Example 9, the permeation rate of ethanol is lower than that in Example 1. This is because the slit opening width and the slit opening length are small, so that the ethanol that has passed through the water collecting cell row suffers a pressure loss at the slit opening. In addition, in Example 6 and Example 8, since the number of filtration cell rows between the collection cell rows is large and more permeation components are concentrated in one water collection row, the opening length should be increased. Reduced the pressure loss. Therefore, it was found that the slit opening width is preferably 10% or more of the inner diameter of the water collecting cell, and the total slit opening length is preferably 3.3% or more of the total length of the monolith type base material.

Next, the thickness of the outer wall will be described. In Example 10, since the outer wall thickness is as thin as 0.9 mm (6 times the partition wall thickness), the membrane area is increased and the ethanol permeation rate is improved as compared with Example 1. As a result, the structure was destroyed at less than 20 MPa. On the other hand, in Example 11, since the outer wall thickness was as thick as 6 mm (40 times the partition wall thickness), the membrane area was relatively reduced and the ethanol permeation rate was lowered. Further, in Example 12, the inner diameter of the filtration cell, the thickness of the partition wall, the thickness of the intermediate layer, and the material density are each the most disadvantageous to the membrane area, and the outer wall thickness is also thickened. The membrane area per unit weight was 0.5 m ² / kg or less, and the permeation rate was significantly reduced. From the above, it was confirmed that the outer wall thickness is preferably 10 times or more and 30 times or less the thickness of the partition wall.

100 Monolith type separation membrane structure 10 Monolith type base material 11 Main body 11S 1st end surface 11T 2nd end surface 11U Outer peripheral surface 12 1st seal 13 2nd seal 14 1st seal 15 2nd seal 20 Intermediate Layer 21 1st intermediate layer 22 2nd intermediate layer 24 Filtration cell 24L Filtration cell row 25 Water collecting cell 25L Water collecting cell row 26 Drainage channel 26a Opening

Claims (10)

A monolith-type separation membrane structure made of a porous ceramic body.
A monolith-type substrate having a plurality of filtration cells continuously connected from the first end face to the second end face,
An intermediate layer formed on the inner surface of the filtration cell and
The separation membrane formed on the inner surface of the intermediate layer and
Equipped with
The inner diameter of each of the plurality of filtration cells excluding the intermediate layer and the separation membrane is 1.0 mm or more and 2.0 mm or less.
The partition wall thickness of the shortest portion of the monolith type substrate between two adjacent filtration cells among the plurality of filtration cells is 0.05 mm or more and less than 0.2 mm.
The thickness of the intermediate layer is 20 μm or more and less than 100 μm.
Monolith type separation membrane structure. The monolith-type base material has a plurality of water collecting cells that are continuous from the first end surface to the second end surface and are sealed at both ends.
The plurality of filtration cells form a plurality of filtration cell rows including two or more filtration cells arranged in a predetermined direction when the first end surface is viewed in a plan view.
The plurality of water collecting cells form a plurality of water collecting cell rows including two or more water collecting cells arranged along the predetermined direction when the first end surface is viewed in a plan view.
Between the two collection cell rows of the plurality of water collection cell rows, two or more and nine or less filtration cell rows of the plurality of filtration cell rows are arranged.
The monolith type separation membrane structure according to claim 1. The monolith-type base material has a plurality of discharge channels penetrating each of the plurality of water collecting cell rows.
Each of the plurality of discharge channels includes an opening that opens on the outer peripheral surface of the monolith type base material.
The width of the opening in the circumferential direction about the axis of the monolith type base material is 10% or more and 80% or less of the inner diameter of the water collecting cell.
The monolith type separation membrane structure according to claim 1 or 2. The length of the opening in the longitudinal direction of the monolith-type substrate is 3.3% or more and 40% or less of the total length of the monolith-type substrate in the longitudinal direction.
The monolith type separation membrane structure according to claim 3. The outer wall thickness of the monolith type base material is 10 times or more and 30 times or less the thickness of the partition wall.
The monolith type separation membrane structure according to any one of claims 1 to 4. Isostatic strength is 20 MPa or more,
The monolith type separation membrane structure according to any one of claims 1 to 5. The area of the plurality of separation membranes per unit volume is 1 m ² / L or more.
The monolith type separation membrane structure according to any one of claims 1 to 6. The area of the plurality of separation membranes per unit weight is 0.5 m ² / kg or more.
The monolith type separation membrane structure according to any one of claims 1 to 7. A method for manufacturing a monolith-type separation membrane structure made of a porous ceramic body.
A step of forming a monolithic molded body using aggregate particles having an average particle size of 5 μm or more and less than 40 μm, and
A step of forming a monolith type base material having a plurality of filtration cells continuously connected from the first end face to the second end face by firing the molded body.
The step of forming an intermediate layer on the inner surface of the filtration cell and
The step of forming a separation film on the inner surface of the intermediate layer and
Equipped with
In the monolith type substrate, the inner diameter of each of the plurality of filtration cells excluding the intermediate layer and the separation membrane is 1.0 mm or more and 2.0 mm or less, and the monolith type substrate among the plurality of filtration cells. The partition wall thickness of the shortest portion is 0.05 mm or more and less than 0.2 mm, and the thickness of the intermediate layer is 20 μm or more and less than 100 μm.
A method for manufacturing a monolith type separation membrane structure. A step of forming a notch for a discharge flow path by cutting the first end surface of the fired monolith-type base material, and
The step of filling the notch with the sealing member and
The step of firing the sealing member and
The method for producing a monolith type separation membrane structure according to claim 9.

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